Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
  • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
  • D06P1/5271—Polyesters; Polycarbonates; Alkyd resins

Definitions

• the inexpensive sulfosuccinic acid and its esters are not thermally stable and release sulfur dioxide at condensation temperatures above 180 ° C. The situation is even more unfavorable with diols containing sulfo groups.
• the invention relates to a water-soluble or dispersible polyester, which is characterized in that it contains phosphonic acid ester groups.
• the invention also relates to a process for the preparation of the polyester containing phosphonic acid ester groups and its use as a leveling aid, and to the leveling aids produced using the polyester according to the invention and processes for uniform dyeing.
• R hydrogen, an aliphatic radical having 1 to 22 carbon atoms, which can also be interrupted one or more times by oxygen, a cycloaliphatic radical having 5 to 8 carbon atoms, phenyl, naphthyl, the phenyl or naphthyl radical can also be substituted by up to 3 alkyl radicals each having 1 to 6 carbon atoms, a phenyl-substituted aliphatic radical having 1 to 12 carbon atoms in the aliphatic radical, which can also be interrupted one or more times by oxygen.
• the polyester according to the invention can be prepared by adding 100 mol% of dibasic acids and / or their derivatives suitable for polyester production, in particular their esters, acid halides or anhydrides with 80 to 140 mol%, preferably 90 to 130 mol%, of dialcohols or their esters lower carboxylic acids are condensed in a manner known per se to an apparent average molecular weight of 800 to 5000, preferably 1500 to 3000, and the starting components are selected such that they are preferably 2.5 to 50%, based on the sum of the chain links Contain 5 to 30%, phosphonic acid groups and / or phosphonic acid ester groups.
• R 1 is a direct bond or a divalent aliphatic, cycloaliphatic, aromatic or araliphatic radical.
• R is preferably a divalent aliphatic radical with 2 to 10 C atoms, a divalent cycloaliphatic radical with 6 to 8 C atoms, a divalent aromatic radical with 6 to 12 C atoms or an araliphatic radical with 6 to 14 C atoms.
• Suitable aliphatic, cycloaliphatic, aromatic and araliphatic dicarboxylic acids are: oxalic, malonic, amber, methylmalonic, glutaric, dimethylmalonic, adipic, pimeline, cork, 2,2-dimethylglutaric, azelaic, Trimethyladipine, sebacin, fumaric, maleic, itacon, citracon, mesacon, traumatin, mucon, 1,2-cyclohexane-dicarbon-, 1,3-cyclohexane-dicarbon-, 1,4-cyclohexane -dicarbon-, norbonandicarbon-, phthalic, isophthalic, terephthalic, 1,4-naphthalene-dicarboxylic, 2,5-naphthalene-dicarboxylic, diphenic acid and acids of the general formula where R is an ortho, meta or para alkylene radical having 2 to 4 carbon atoms, z.
• Aromatic dicarboxylic acids, isophthalic and terephthalic acid are preferred because of their difficult saponifiability.
• the carbon skeleton of the dicarboxylic acids in question can also be interrupted by heteroatoms, such as oxygen or sulfur, or hetero groups, such as —SO 2 -.
• heteroatoms such as oxygen or sulfur
• hetero groups such as —SO 2 -.
• Examples include diglycolic acid, thiodiglycolic acid, thiodipropionic acid, 4,4'-oxy, dibenzoic acid, 4,4'-sulfonyldibenzoic acid and where R 2 is an alkylene radical having 2 to 4 carbon atoms and the side chain can be ortho, meta or para to the carboxyl group of the core.
• the phosphonic acids mentioned above under A b) have the general formula and lead the phosphonic acid ester group VII and the chain link VIIa into the polyester.
• R has the meaning already mentioned.
• Suitable phosphonic acids are: methane, ethane, n-propane, i-propane, n-butane, n-butene-2, i-butane, n-octane - , i-octane, decane -, Dodecane, octadecane, nonadecane, docosane-phosphonic acid, cyclopentane, cyclohexane, benzene, a-naphthalene, ß-naphthalene-phosphonic acid, 3-oxapentane-phosphonic acid, 4-oxaheptane, 4,8-dioxaundecane-phosphonic acid , Phosphonic acids of the general formula where R 3 is an alkylene radical having 1 to 12 carbon atoms, which can also be interrupted one or more times by oxygen, for example benzyl-, phenethyl-phosphonic acid C 6 H 5 CH
• the phosphonic acids mentioned can also be in the form of their derivatives, in particular in the form of their mono- or di-esters with lower, i.e. easily distillable monoalcohols, preferably those with 1 to 4 carbon atoms or the dialcohols still to be mentioned, or in the form of their halides, in particular chlorides or in the form of their anhydrides.
• the phosphorous acid is expediently used only in the form of its esters, in particular its esters with alcohols having 1 to 4 carbon atoms, e.g. used as diethyl phosphite.
• diols examples include: ethylene glycol; 1,2-propanediol and 1,3-propanediol (trimethylene glycol); Butanediols, especially 1,4-butanediol; Pentanediols such as pentanediol-1,5; Hexanediols, especially 1,6-hexanediol; Decanediol-1.10; Diethylene glycol, 1,2-ethylene propylene glycol; Ethylene propylene glycol 1,3; Dipropylene glycol; Triethylene glycol, tetraethylene glycol; Tripropylene glycol; Polyethylene glycol up to a molecular weight of 10,000; Polypropylene glycol up to a molecular weight of 10,000 or higher; Polyethylene-polypropylene mixed glycols (so-called "Pluronics”) up to a molecular weight of 10,000 or higher; Bis (4-hydroxybutyl) ether; 2,
• the representatives of the diols mentioned for B, a) can also be used as esters with volatile carboxylic acids, e.g. Formic, acetic or propionic acid can be used.
• the compounds of the general formulas XIII and / or XIV are advantageously used as mixtures. These compounds can also be used as esters with volatile carboxylic acids.
• the dialcohols of group B are selected so that at least half of the molar amount used consists of water-soluble representatives containing ether groups, which group in the finished polyester install, where r is a number from 1 to 230, t is a number from 1 to 175 and u is a number from 1 to 100.
• r is a number from 1 to 230
• t is a number from 1 to 175
• u is a number from 1 to 100.
• w, x, y are equal to or greater than 1 and as large numbers, a ß d grouping a molecular weight of up to 10,000 obtained from.
• Diethylene glycol and dipropylene glycol are preferred.
• hydroxy acids (C) can be a) hydroxycarboxylic acids and b) hydroxyphosphonic acids or mixtures of the two.
• R 7 represents a divalent aliphatic, cycloaliphatic or araliphatic radical.
• R 7 denotes a divalent aliphatic radical having 1 to 10 carbon atoms, a divalent cycloaliphatic radical having 6 to 11 carbon atoms, a divalent araliphatic radical having 8 to 12 carbon atoms, the araliphatic radical being the aliphatic part of aromatic part can also be separated by a heteroatom and / or the aliphatic part can also be interrupted by one or more heteroatoms.
• Oxygen is particularly suitable as the heteroatom.
• Suitable hydroxycarboxylic acids are glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 5-hydroxypentane-3-acid, mandelic acid, 3-hydroxymethyl-cyclohexane-carboxylic acid, 4-hydroxynethyl-cyclohexane carboxylic acid, 6-hydroxymethyl-decalin -carboxylic acid- (2), meta- and para-hydroxyethoxy-benzoic acid as representatives of compounds of the general formula where R 5 , R 6 and s have the meanings already mentioned.
• Other suitable hydroxycarboxylic acids have the general formula
• esters of hydroxycarboxylic acids are: lactic acid methyl ester, lactic acid ethyl ester, 4-hydroxybutyric acid methyl ester, mandelic acid ethyl ester, para-hydroxyethoxy-benzoic acid methyl ester.
• suitable internal esters of hydroxycarboxylic acids are butyrolactone and valerolactone.
• Suitable internal esters of hydroxyphosphonic acid are 2-oxo-1,3,2-dioxaphospholanes of the general formula wherein R, R 5 and R 6 have the meanings already mentioned.
• Suitable representatives of such hydroxyphosphonic acids and phospholanes are, for example
• polyester it is of course also possible to use low precondensates or oligomers from the abovementioned components, for example instead of the monomeric components A, B or C. where R 6 and R 5 have the meanings already mentioned.
• the starting products containing phosphonic acid groups or phosphonic acid ester groups are easily accessible and are in part inexpensive commercial products (e.g. from Hoechst AG, Germany). Like the other starting products, they can easily be prepared by the processes known for the respective class of compounds.
• the preparation of compounds of the general formulas XIV, XV, XVIII and XIX is described in DE-OS 27 26 478.
• the production of the polyester according to the invention by condensation of the starting components is, as usual, at an elevated temperature of 100 to 280 ° C, in particular 150 to 230 ° C, preferably under an atmosphere of an inert gas, such as nitrogen or carbon dioxide, and / or under reduced pressure Pressure and expediently carried out with stirring, the volatile condensation products (water and / or alcohols) and any excess starting components, usually a diol, being distilled off. If normal pressure is used, it may be expedient to apply a vacuum of, for example, 10 to 30 mbar at the end of the condensation and, if appropriate, then a vacuum of about 1 to 3 mbar or, if appropriate, even below this in order to largely remove the volatile products.
• an inert gas such as nitrogen or carbon dioxide
• the condensation normally takes 3 to 20 hours and is carried out until the desired apparent average molecular weight of 800 to 5000, preferably 1500 to 3000, is reached.
• the starting materials used for the condensation can all be mixed first and then condensed together. With this procedure, the building blocks are available in statistical distribution in the product.
• the products according to the invention can also be obtained by first precondensing only some of the starting materials and then subsequently condensing the rest with the precondensate in any order and at any time interval.
• products with different distribution of the individual building blocks can be made using the same starting materials are produced, which can also differ in their application properties. Different application properties can be obtained particularly easily by condensation of different degrees, that is to say by products of different molecular weights.
• alkali metal hydroxides such as sodium or potassium hydroxide, or alkali metal alcoholates, such as sodium methylate or ethylate
• alkaline earth metal oxides or hydroxides such as, for example, the corresponding calcium or magnesium compounds, and also zinc or cadmium oxide
• salts of organic carboxylic acids can be used as esterification or transesterification catalysts , such as sodium, calcium, manganese or zinc acetate or formate, organic titanium compounds, especially the titanium alcoholates, such as titanium isopropylate or titanium butylate and the like. be used.
• the amounts to be used depend primarily on the effectiveness of the particular catalyst. The amount of catalyst is usually kept as low as possible. Acidic catalysts are not very suitable because they convert the preferred diol diethylene glycol into dioxane and thus largely remove them from the chain-forming reactions.
• the apparent average molecular weight is determined in a vapor pressure osmometer in dimethylformamide as the solvent.
• the measured value is a sufficiently precise criterion for characterizing the polyesters according to the invention. (The determination of the molecular weight in the vapor pressure osmometer is described by S. Kume and H. Kobayashi in Makromol. Chem. 79 (1964), 1 to 7).
• polyesters according to the invention are suitable for many purposes, e.g. as water-soluble adhesives, as sizing agents, as hair setting agents, but above all as leveling and dispersing agents when dyeing synthetic fibers, especially polyester fibers and polyester blends with cellulose and wool using the pull-out method.
• the polyesters according to the invention are more economical to produce, since the starting materials containing phosphonic acid are cheaper and easier to produce than the sulfone monomers currently used, such as dimethyl sulfopropoxyisophthalate.
• the polyesters of the invention provide a hitherto unknown ability to modify the properties of water-soluble polyester, thus allowing the manufacturing l ung of products with completely new properties.
• the radicals for R 8 and R 9 can also be substituted, in particular by hydroxyl.
• the required ethoxylation products of the general formula XXII are in part commercially available as emulsifiers and are obtained in a manner known per se by reacting compounds R OH with 5 to 50 moles
• Suitable starting products for the reaction with ethylene oxide are, for example, n-hexanol, n-heptanol, Isooctanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, caproic acid, capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, oleic acid, ricinoleic acid, linoleic acid and the monoesters of the aforementioned acids (eg 1,4-butanediol) 4-hydroxybutyl caproate, 4-hydroxybutyl laurate, 4-hydroxybutyl palmitate, 4-hydroxybutyl stearate, 4-hydrobutyl oleate, 4-hydroxybutyl ricinoleate, 4-hydroxybutyl linolate, also castor oil, phenol mandelic acid, salicylic acid Naphthol
• the improved leveling agent is prepared in accordance with possibility a) above.
• the pH is slightly acidic. It is then expedient to adjust the pH of the leveling agent to a pH of 6 to 7 by stirring in an inorganic or organic base, such as, for example, potassium or sodium hydroxide solution or ammonia. In this case, all or part of the acid groups present are converted into the corresponding salts.
• a polyester according to the invention is reacted with a compound of the general formula XXII at temperatures from 100 to 300 ° C., preferably 150 to 250 ° C., ie heated to this temperature and melted together.
• the reaction times are 10 minutes to 10 hours, preferably 2 to 5 hours.
• the reaction components are melted together without the use of a solvent or diluent.
• the reaction can be carried out at normal pressure, but the use of negative pressure is advisable.
• the polycondensation is preferably carried out at a pressure of about 0.5 to 30 mbar carried out.
• the volatile products formed during the reaction are distilled off.
• the reaction mixture is expediently stirred during the reaction.
• the reaction between the polyester and the ethoxylation component usually takes place in the presence of one of the esterification or transesterification catalysts already mentioned. However, the polycondensation can also be carried out without a catalyst (usually if the reaction time is increased).
• the polycondensates obtained by reacting the polyester and compound XII are tough melts which, when diluted with water, give clear to opalescent viscous solutions or dispersions. When diluting with water, both the melt in water and water can be stirred into the polycondensate.
• the aqueous solutions of the polycondensate generally have a weakly acidic pH. It is expedient to prepare the aqueous solutions by stirring in an inorganic or organic base, e.g. Adjust sodium or potassium hydroxide solution or ammonia to pH values from 6 to 7.
• polyesters according to the invention and in particular their mixtures with a compound of the general formula XXII and in particular their condensation products with a compound of the general formula XXII are outstandingly suitable as leveling agents in the dyeing of materials from synthetic fibers or their mixtures with natural fibers with disperse dyes.
• a high stability of the dye liquors is achieved, and completely level dyeings with a high dye yield are obtained. Excellent results are obtained even with goods that are difficult to dye, such as packages, or dyes that are difficult to dye. Rapid dyeing processes give particularly good results. In such rapid dyeing processes, the goods to be dyed are suddenly offered relatively large amounts of dye at temperatures of approximately 130 ° C. The resulting risk of irregularities is avoided by using the polyester according to the invention, preferably a mixture of the polyester, with a compound of the general formula XXII or preferably a polyester according to the invention with a condensed compound of the general formula XXII.
• the dyeing baths are prepared in the customary manner at 50 to 60 ° C. and adjusted to pH 4 to 6 by means of pH-regulating substances.
• the polyester according to the invention preferably a mixture of the polyester, with a compound of the general formula XXII or preferably a polyester according to the invention with a condensed compound of the general formula XXII is advantageously in the form of a solution in amounts of 0.02 to 5 g / l, preferably 0 , 2 to 2 g / 1 (based on 100 siges polycondensate) added.
• the predisper gated, water-insoluble disperse dye and the material to be dyed and heated to the required dyeing temperature and dyed for the usual dyeing time.
• the dyeings are finished in a known manner, for example by reductive aftertreatment.
• the liquor is produced separately from the material to be colored with the addition of the polyester according to the invention, preferably a mixture of the polyester, with a compound of the general formula XXII or preferably a polyester according to the invention with a condensed compound of the general formula XXII.
• the liquor heated to the dyeing temperature of 120 to 130 ° C, is then quickly brought into contact with the material to be dyed. If the so-called sluice technique is used, the polycondensation product according to the invention can also be added to the dyebath before adding the dye dispersion.
• additives according to the invention can also be used in other solvents or be expedient, in particular a partial addition of other solvents, preferably alcohols, such as methanol, ethanol or isopropanol, or else dipolar aprotic solvents, such as dimethylformamide or dimethyl sulfoxide.
• solvents preferably alcohols, such as methanol, ethanol or isopropanol, or else dipolar aprotic solvents, such as dimethylformamide or dimethyl sulfoxide.
• aliphatic also used in connection with the term araliphatic in the context of the present invention stands in particular for alkenyl or alkenylene, but especially for alkyl or alkylene radicals.
• Cycloaliphatic radicals are in particular cycloalkyl or cycloalkylene radicals.
• Aromatic radicals, also in connection with the name araliphatic, are in particular those which contain a radical derived from benzene or naphthalene.
• Polyester solutions with similarly good properties are obtained if the homologous methane, ethane or n-butane-phosphonic acid ester is used in an aliquot instead of propanephosphonic acid bis- ( ⁇ -hydroxyethyl ester).
• a similar leveling agent as in Example 2 is obtained by analogous polycondensation of 20 mol% ethanephosphonic acid, 40 mol% DMT; 40 mole% IPA; 100 mol% DEG and 10 mol% PEG 600, MW 1640.
• a similar leveling aid as in Example 2 is also obtained by analogous polycondensation of 20 mol% methanephosphonic acid, 80 mol% cyclohexane-1,4-dicarboxylic acid, 100 mol% DPG and 5 mol% PEG 3000, MW 1710.
• 396 g of a light-colored melt of MG 2060 are obtained, which are diluted to 1980 g with water and about 17 g of 27% sodium hydroxide solution and at the same time neutralized. Most of the turbidity that is still present can be completely removed by stirring with 1 to 2% diatomaceous earth and pressing on a filter press. A clear, only slightly yellowish 20% solution is obtained, which is outstandingly suitable as a leveling agent for dyeing polyester / wool with disperse dyes.
• the MW of this product is 2040.
• Example 8 Practically the same product as in Example 8 is obtained when using the aliquot of 2-n-decyl-2-oxo-1,3,2-dioxaphospholane instead of monomethyl mono-hydroxyethyl decanephosphonate.
• Polyesters according to the invention of the following percentage composition can also be produced in an analogous manner:
• a vacuum of 10 to 30 mbar is then applied at 220 to 225 ° C. for a further 4 hours, and finally a fine vacuum of approx. 1 mbar for a period of 2 hours.
• 118 g of pale melt residue of MG 1680 are obtained, which can be easily diluted to 590 g with water and 7 g of 27% sodium hydroxide solution to give a 20% neutral solution.
• an aliquot of benzene phosphonic acid dimethyl ester or cyclohexane-phosphonic acid dimethyl ester can also be used without significantly changing the properties of the polycondensate.
• a similar water-soluble polyester is also obtained if, in Example 9, instead of 12.4 g of monoethylene glycol, an aliquot of 1,3-propanediol, 1,6-hexanediol or 1,3-2,2'-dimethylpropanediol is used.
• the same product is also obtained if the corresponding amount of the oxyethylation product of castor oil is homogeneously stirred in (preferably at approx. 120 ° C) for water-free melting of the polyester according to Example 10 (before dilution with water) and only then with water diluted to a 30% setting and neutralized with a little sodium hydroxide solution.
• Example 15 the additives mentioned under a to e in Example 15 can also be condensed in place of Emulsogen EL in the procedure of Example 16.
• Muffles made of textured polyester yarns are flowed through on an HT dyeing machine at a liquor ratio of 1:10 with a liquor of 130 ° C. which consists of soft water of pH 4.5 (adjusted with acetic acid) and 0.5 g / 1 of a linear, water-soluble polyester with a molecular weight of 2000, which had been prepared according to Example 10.
• the flow rate through the muff is 20 1 / kg per minute. After 30 minutes of treatment at 130 ° C., the mixture is cooled, the liquor is drained and reductively cleaned.
• Example 17 The procedure is as in Example 17, but using the linear water-soluble polyester according to Example 1. The dyeing is carried out at 130 ° C. for 30 minutes and a completely level brown color is also obtained.
• Example 17 When Example 17 is repeated, a leveling aid prepared according to Example 14 is used instead of the polyester produced according to Example 10. A comparable result is already obtained with 0.4 g / l of the leveling aid.
• Example 17 When Example 17 is repeated, a leveling agent prepared according to Example 15e is used instead of the polyester produced according to Example 10. A comparable result is already obtained with 0.38 g / 1 of the leveling aid.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyesters Or Polycarbonates (AREA)
• Coloring (AREA)

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• 1979
  • 1979-01-10 DE DE19792900686 patent/DE2900686A1/de active Granted
• 1980
  • 1980-01-07 US US06/110,343 patent/US4314052A/en not_active Expired - Lifetime
  • 1980-01-07 EP EP80100065A patent/EP0013564A1/de not_active Withdrawn
  • 1980-01-08 BR BR8000088A patent/BR8000088A/pt unknown
  • 1980-01-09 ZA ZA00800119A patent/ZA80119B/xx unknown
  • 1980-01-09 JP JP61780A patent/JPS5594932A/ja active Pending
  • 1980-01-09 ES ES487557A patent/ES8102162A1/es not_active Expired

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